CN108706579B - Method for preparing fluorine-doped graphene quantum dots - Google Patents
Method for preparing fluorine-doped graphene quantum dots Download PDFInfo
- Publication number
- CN108706579B CN108706579B CN201810809646.2A CN201810809646A CN108706579B CN 108706579 B CN108706579 B CN 108706579B CN 201810809646 A CN201810809646 A CN 201810809646A CN 108706579 B CN108706579 B CN 108706579B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- graphene quantum
- quantum dots
- gas
- doped graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 61
- 239000011737 fluorine Substances 0.000 claims abstract description 61
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002096 quantum dot Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 35
- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 47
- 239000010453 quartz Substances 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910052724 xenon Inorganic materials 0.000 claims description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006552 photochemical reaction Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing fluorine-doped graphene quantum dots, and relates to the field of production and preparation of graphene quantum dots. The method utilizes the photochemical principle, directly dopes the fluorine element into the graphene quantum dot powder by using a photochemical method, can control the fluorine doping concentration by controlling the mass ratio of the xenon difluoride to the graphene quantum dot, is simple and easy to operate, can complete the doping only within minutes to tens of minutes, and overcomes the defect that other impurities are easily introduced by using a traditional method for doping fluorine-containing organic matter as a fluorine source.
Description
Technical Field
The invention relates to the field of production and preparation of graphene quantum dots, in particular to a method for preparing fluorine-doped graphene quantum dots.
Background
Graphene quantum dots, as a novel low-dimensional graphite material, have attracted attention in recent years due to their excellent light resistance, good biocompatibility, good tunable photoluminescence properties, peculiar up-conversion characteristics, excellent catalytic activity, chemical inertness and other properties. The method has attracted extensive attention and research heat in the fields of nano science, nano technology and the like, and has been widely applied to the aspects of super capacitors, solar cells, biological calibration and imaging, ultra-sensitive sensors and detectors, fluorescent probes and the like. Due to special optical properties, electronic properties, chemical stability, spin properties, etc., Graphene Quantum Dots (GQDs) have become a hot spot in many research fields of materials. Doping is an effective means for changing the energy level structure, optical properties and electrical properties of materials. Other elements are doped into the graphene quantum dots, so that an effective means for realizing the fluorescence regulation of the graphene quantum dots is realized.
Doping other impurity atoms into the graphene quantum dots is an important way for regulating and controlling the photoluminescence performance of the graphene quantum dots, and the application of the doped graphene quantum dots is widened by preparing the doped graphene quantum dots. Because fluorine atoms have stronger electronegativity, the band gap of the graphene quantum dots can be effectively regulated and controlled by doping fluorine elements into the graphene quantum dots, and the method is an important way for improving the material performance. At present, related literature reports that a hydrothermal method is used for preparing fluorine-doped graphene quantum dots, but the method for preparing fluorinated graphene quantum dots has long reaction time and high reaction temperature, and is not beneficial to rapid mass preparation of fluorine-doped graphene quantum dots. There are also related documents reporting methods for preparing fluorinated graphene quantum dots by cutting fluorinated graphene through a hydrothermal method, but these methods are cumbersome in process and require expensive fluorinated graphene as a raw material to prepare the fluorinated graphene quantum dots. In addition, compared with fluorinated graphene, the fluorine content of the prepared fluorinated graphene quantum dot is reduced and is difficult to regulate and control.
The application number 201510749594.0 discloses a fluorine-doped graphene quantum dot and a preparation method thereof, wherein fluorine-doped carbon fibers are prepared by combining a hydrothermal synthesis method, and the fluorine-doped graphene quantum dot is successfully prepared by ultrasonic liquid phase stripping. But high-temperature reaction and separation are needed, the process is complex, and impurities are introduced, so that the later use of the material is not facilitated. The Chinese patent with the application number of 201610117401.4 discloses a preparation method of fluorine-doped graphene quantum dots with excellent optical performance, wherein the fluorine-doped graphene quantum dots are maintained at 180 ℃ in a high-temperature reaction kettle for gas-phase reaction for 24 hours, and after natural cooling, the excess unreacted XeF is dried and removed at 70 DEG C2And preparing the fluorine-doped graphene quantum dots with excellent optical properties. However, this method has a long reaction time and cannot control the doping concentration, although the preparation process is simple. Therefore, the market needs urgently to explore a preparation method of the fluorine-doped graphene quantum dot, which has the advantages of simple process, high product purity and low cost.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for preparing a fluorine-doped graphene quantum dot, which overcomes the disadvantage that other impurities are easily introduced in the conventional doping method using a fluorine-containing organic substance as a fluorine source, and can prepare a high-purity fluorine-doped graphene quantum dot by using a photochemical principle and reacting a fluorine radical generated by ultraviolet irradiation with the graphene quantum dot.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing fluorine-doped graphene quantum dots comprises the steps of taking graphene quantum dots as raw materials, taking xenon difluoride as a fluorine source, heating and decomposing the xenon difluoride to generate fluorine gas and xenon, driving the fluorine gas and the xenon to enter a photochemical reaction chamber, irradiating the graphene quantum dots and the fluorine gas in the photochemical reaction chamber by using ultraviolet light, generating fluorine radicals with high activity by the fluorine gas under the irradiation of the ultraviolet light, and reacting the fluorine radicals with the graphene quantum dots under the irradiation of the ultraviolet light to obtain the high-purity fluorine-doped graphene quantum dots.
Preferably, the wavelength of the ultraviolet light is 300nm to 380 nm.
Preferably, the wavelength of the ultraviolet light is 360 nm.
Preferably, the power of the ultraviolet light is 300 w-800 w.
Preferably, the ultraviolet light is 500 w.
Preferably, the ultraviolet irradiation time is 5min to 15 min.
Preferably, the photochemical reaction chamber is a quartz boat.
Preferably, the xenon difluoride is heated to 50-80 ℃ and decomposed to generate fluorine gas and xenon gas.
Preferably, argon is used to drive fluorine and xenon into the photochemical reaction chamber.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. according to the preparation method, a photochemical method is adopted, fluorine free radicals generated by irradiating fluorine gas with ultraviolet light are in point contact reaction with the graphene quantum dots to form relatively stable carbon-fluorine bonds, and fluorine elements are doped into the graphene quantum dots. The difficulty that fluorine is difficult to be doped into the graphene quantum dots is overcome. Meanwhile, the method also overcomes the defect that other impurities are easily introduced in the traditional doping method using fluorine-containing organic matters as fluorine sources, and can prepare high-purity fluorine-doped graphene quantum dots.
2. According to the preparation method, the fluorine doping concentration of the graphene quantum dots can be regulated and controlled by controlling the mass ratio of the graphene quantum dots to xenon difluoride, so that different requirements are met. The application of the graphene quantum dot in the fields of fluorescence labeling, photocatalysis, nonlinear optics, photoelectrons and the like is expanded, and the requirements on graphene quantum dots with different fluorine contents can be met.
3. The preparation method is simple and easy to operate, and the doping time can be completed only by minutes to tens of minutes. Compared with the existing method for preparing the fluorine-doped graphene quantum dots, the method has the advantages of easy operation and control in experiments, shorter doping time and no need of taking expensive fluorinated graphene as a raw material.
Drawings
Fig. 1 is an X-ray photoelectron energy spectrum corresponding to the graphene quantum dot of the present invention and the fluorine-doped graphene quantum dot in examples 1 to 4;
FIG. 2 is a schematic view of an apparatus for preparing fluorine-doped graphene quantum dots according to the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) morphology corresponding to the graphene quantum dots of the present invention;
fig. 4 is a Transmission Electron Microscope (TEM) morphology corresponding to the fluorine-doped graphene quantum dot prepared in example 2 of the present invention;
FIG. 5 is a fluorescence spectrum corresponding to the Graphene Quantum Dots (GQDs) of the present invention, and a photograph of an aqueous solution embedded in a corresponding sample under 365nm wavelength ultraviolet light irradiation;
fig. 6 is a fluorescence spectrum corresponding to the fluorine-doped graphene quantum dots (F-GQDs) prepared in example 2 of the present invention, and a photograph of an aqueous solution embedded in a corresponding sample under the irradiation of ultraviolet light with a wavelength of 365 nm;
in the figure, 1-inert gas tank, 2-oil bath, 3-quartz round bottom flask, 4-valve, 5-ultraviolet lamp, 6-quartz boat, 7-quartz tube, 8-tail gas treatment device.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An apparatus for preparing fluorine-doped graphene quantum dots, as shown in fig. 2, comprises an inert gas tank 1, an oil bath pot 2, a quartz round-bottom flask 3, a valve 4, an ultraviolet lamp 5, a quartz boat 6, a quartz tube 7 and a tail gas treatment device 8, wherein the inert gas tank 1 is an argon gas tank, the quartz boat 6 is located inside the quartz tube 7, and graphene quantum dots are placed in the quartz boat 6; the ultraviolet lamp 5 is arranged above the quartz tube 8 and corresponds to the quartz boat 6.
Connecting an argon tank 1 with the front end of a quartz round-bottom flask 3 containing xenon difluoride by using a polytetrafluoroethylene tube, soaking the quartz round-bottom flask 3 in an oil bath pot 2, connecting an air inlet of a quartz tube 7 with an opening at the rear end of the quartz round-bottom flask 3 by using the polytetrafluoroethylene tube, and connecting an air outlet of the quartz tube 7 with a round-bottom flask 8 containing a NaOH solution by using the polytetrafluoroethylene tube. Xenon difluoride is filled in the quartz round-bottom flask 3.
The tail gas treatment device 8 is a flask filled with NaOH solution, plays a role in absorbing redundant fluorine gas, and avoids environmental pollution.
Example 1
A method for preparing fluorine-doped graphene quantum dots comprises the following steps:
s1, devices for preparing fluorine-doped graphene quantum dots are sequentially installed, 200mg of xenon difluoride is weighed and added into a quartz round-bottom flask 3, 100mg of graphene quantum dot samples are weighed and loaded into a quartz boat 6, the head of a quartz tube 7 is detached, and the quartz boat 6 is slowly placed into the quartz tube 7.
Opening a valve of an argon tank 1, and introducing argon to remove air in the whole experimental device system; during this process the oil bath pan 2 was heated to 60 ℃. The xenon difluoride is decomposed under heating to generate fluorine gas and xenon gas, and the fluorine gas and the xenon gas reach the quartz tube 7 where the sample is located under the driving of the argon gas.
S2, turning on a switch of the ultraviolet lamp 5, irradiating the graphene quantum dots in the quartz tube 7 for 10min by the ultraviolet lamp 5, wherein fluorine gas generates fluorine free radicals with high activity under illumination, and the fluorine free radicals react with the graphene quantum dots to obtain high-purity fluorine-doped graphene quantum dots. The ultraviolet lamp is a high-pressure mercury lamp, and the power of the high-pressure mercury lamp is 500 w.
As shown in fig. 1, F-GQDs1 corresponds to an X-ray photoelectron spectrum, and as can be seen from the X-ray photoelectron spectrum, the prepared fluorine-doped graphene quantum dot significantly increases the peak of the F element, and by calculating that the content of F is 16.25%, except for the increase of the peak of the F element, no signal peak of other impurities is added, which indicates that the method can be used to successfully prepare the fluorine-doped graphene quantum dot, and prepare a high-purity fluorine-doped graphene quantum dot sample. The components and contents of the elements before and after fluorine doping of the graphene quantum dots are shown in table 1 below.
Example 2
A method for preparing fluorine-doped graphene quantum dots comprises the following steps:
s1, devices for preparing fluorine-doped graphene quantum dots are sequentially installed, 500mg of xenon difluoride is weighed and added into a quartz round-bottom flask 3, 100mg of graphene quantum dot samples are weighed and loaded into a quartz boat 6, the head of a quartz tube 7 is detached, and the quartz boat 6 is slowly placed into the quartz tube 7.
Opening a valve of an argon tank 1, and introducing argon to remove air in the whole experimental device system; during this process the oil bath pan 2 was heated to 60 ℃. The xenon difluoride is decomposed under heating to generate fluorine gas and xenon gas, and the fluorine gas and the xenon gas reach the quartz tube 7 where the sample is located under the driving of the argon gas.
S2, turning on a switch of the ultraviolet lamp 5, irradiating the graphene quantum dots in the quartz tube 7 for 10min by the ultraviolet lamp 5, wherein fluorine gas generates fluorine free radicals with high activity under illumination, and the fluorine free radicals react with the graphene quantum dots to obtain high-purity fluorine-doped graphene quantum dots. The ultraviolet lamp is a high-pressure mercury lamp, and the power of the high-pressure mercury lamp is 500 w.
As shown in figure 1, GQDs and F-GQDs2 correspond to an X-ray photoelectron spectrum, and the X-ray photoelectron spectrum shows that the prepared fluorine-doped graphene quantum dot obviously increases the peak of an F element, and the content of F is calculated to be 28.07%, except the increased peak of the F element, signal peaks of other impurities are not increased, which indicates that the method can be used for successfully preparing the fluorine-doped graphene quantum dot and preparing a high-purity fluorine-doped graphene quantum dot sample. The components and contents of the elements before and after fluorine doping of the graphene quantum dots are shown in table 1 below.
As shown in fig. 3 and 4, the transmission electron microscope topography of the graphene quantum dots GQDs and the fluorine-doped graphene quantum dots F-GQDs are embedded with high resolution transmission electron microscope pictures respectively. It can be seen from the figure that the graphene quantum dots still maintain a good lattice structure after being doped with fluorine.
Fig. 5 and 6 are fluorescence spectra of the graphene quantum dots and the fluorine-doped graphene quantum dots. It can be seen that the graphene quantum dots can emit bright yellow fluorescence (525nm) independent of the excitation wavelength at the excitation wavelength of 280nm-460nm, and the fluorine-doped graphene quantum dots can emit bright blue fluorescence (453nm) independent of the excitation wavelength at the excitation wavelength of 280nm-380 nm. This shows that, compared with the graphene quantum dot, the fluorescence of the prepared fluorine-doped graphene quantum dot generates a blue shift of 72nm, which marks that the fluorescence regulation of the graphene quantum dot is realized. It can be seen that the aqueous solutions of the samples corresponding to the graphene quantum dots and the fluorine-doped graphene quantum dots can respectively emit bright yellow fluorescence and blue fluorescence under the irradiation of 365nm wavelength ultraviolet light.
Example 3
A method for preparing fluorine-doped graphene quantum dots comprises the following steps:
s1, devices for preparing fluorine-doped graphene quantum dots are sequentially installed, the devices for preparing the fluorine-doped graphene quantum dots are sequentially installed, 1000mg of xenon difluoride is weighed and added into a quartz round-bottom flask 3, 100mg of graphene quantum dot samples are weighed and loaded into a quartz boat 6, the head of a quartz tube 7 is detached, and the quartz boat 6 is slowly placed into the quartz tube 7.
Opening a valve of an argon tank 1, and introducing argon to remove air in the whole experimental device system; during this process the oil bath pan 2 was heated to 60 ℃. The xenon difluoride is decomposed under heating to generate fluorine gas and xenon gas, and the fluorine gas and the xenon gas reach the quartz tube 7 where the sample is located under the driving of the argon gas.
S2, turning on a switch of the ultraviolet lamp 5, irradiating the graphene quantum dots in the quartz tube 7 for 10min by the ultraviolet lamp 5, wherein fluorine gas generates fluorine free radicals with high activity under illumination, and the fluorine free radicals react with the graphene quantum dots to obtain high-purity fluorine-doped graphene quantum dots. The ultraviolet lamp is a high-pressure mercury lamp, the power of the high-pressure mercury lamp is 500w, and the wavelength is 360 nm.
As shown in fig. 1, F-GQDs3 corresponds to an X-ray photoelectron spectrum, and as can be seen from the X-ray photoelectron spectrum, the prepared fluorine-doped graphene quantum dot significantly increases the peak of the F element, and by calculating that the content of F is 52.87%, except for the increase of the peak of the F element, no signal peak of other impurities is added, which indicates that the method can be used to successfully prepare the fluorine-doped graphene quantum dot, and prepare a high-purity fluorine-doped graphene quantum dot sample.
The components and contents of the elements before and after fluorine doping of the graphene quantum dots are shown in table 1 below.
Table 1: elemental components and contents of graphene quantum dots before and after fluorine doping
Example 4
A method for preparing fluorine-doped graphene quantum dots comprises the following steps:
s1, devices for preparing fluorine-doped graphene quantum dots are sequentially installed, 500mg of xenon difluoride is weighed and added into a quartz round-bottom flask 3, 100mg of graphene quantum dot samples are weighed and loaded into a quartz boat 6, the head of a quartz tube 7 is detached, and the quartz boat 6 is slowly placed into the quartz tube 7.
Opening a valve of an argon tank 1, and introducing argon to remove air in the whole experimental device system; during this process the oil bath pan 2 was heated to 80 ℃. The xenon difluoride is decomposed under heating to generate fluorine gas and xenon gas, and the fluorine gas and the xenon gas reach the quartz tube 7 where the sample is located under the driving of the argon gas.
S2, turning on a switch of the ultraviolet lamp 5, irradiating the graphene quantum dots in the quartz tube 7 for 5min by the ultraviolet lamp 5, wherein fluorine gas generates fluorine free radicals with high activity under illumination, and the fluorine free radicals react with the graphene quantum dots to obtain high-purity fluorine-doped graphene quantum dots. The wavelength of the ultraviolet lamp is 300nm, and the power of the ultraviolet lamp is 600 w.
By calculating that the content of F is 19.25%, except the peak of the element F is increased, signal peaks of other impurities are not increased, and the method is used for successfully preparing the fluorine-doped graphene quantum dot and preparing a high-purity fluorine-doped graphene quantum dot sample. Indicating that in the case of xenon difluoride quantification, the illumination time also affects the amount of fluorine doping.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (7)
1. The method for preparing the fluorine-doped graphene quantum dot is characterized in that the graphene quantum dot is used as a raw material, xenon difluoride is used as a fluorine source, xenon difluoride is heated and decomposed to generate fluorine gas and xenon gas, the fluorine gas and the xenon gas are driven to enter a photochemical reaction chamber, then the fluorine gas and the graphene quantum dot in the photochemical reaction chamber are irradiated by ultraviolet light, the fluorine gas generates fluorine free radicals with high activity under the irradiation of the ultraviolet light, and the fluorine free radicals react with the graphene quantum dot under the irradiation of the ultraviolet light to obtain the high-purity fluorine-doped graphene quantum dot;
the wavelength of the ultraviolet light is 300 nm-380 nm; the ultraviolet light irradiation time is 5-15 min; the mass ratio of the graphene quantum dots to the xenon difluoride is 1: 1-10.
2. The method for preparing fluorine-doped graphene quantum dots according to claim 1, wherein the wavelength of the ultraviolet light is 360 nm.
3. The method for preparing fluorine-doped graphene quantum dots according to claim 1, wherein the ultraviolet light power is 300 w-800 w.
4. The method for preparing fluorine-doped graphene quantum dots according to claim 3, wherein the ultraviolet light power is 500 w.
5. The method of claim 1, wherein the photochemical reaction chamber is a quartz boat.
6. The method for preparing fluorine-doped graphene quantum dots according to claim 1, wherein xenon difluoride is heated to 50-80 ℃ and decomposed to generate fluorine gas and xenon gas.
7. The method for preparing fluorine-doped graphene quantum dots according to claim 1, wherein argon gas is used to drive fluorine gas and xenon gas into the photochemical reaction chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810809646.2A CN108706579B (en) | 2018-07-23 | 2018-07-23 | Method for preparing fluorine-doped graphene quantum dots |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810809646.2A CN108706579B (en) | 2018-07-23 | 2018-07-23 | Method for preparing fluorine-doped graphene quantum dots |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108706579A CN108706579A (en) | 2018-10-26 |
| CN108706579B true CN108706579B (en) | 2020-11-10 |
Family
ID=63875246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810809646.2A Active CN108706579B (en) | 2018-07-23 | 2018-07-23 | Method for preparing fluorine-doped graphene quantum dots |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108706579B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518552B (en) * | 2019-09-10 | 2021-08-10 | 安徽大学 | Preparation of fluorine-containing graphene quantum dots and application of fluorine-containing graphene quantum dots as photodynamic therapy photosensitizer |
| CN115092909B (en) * | 2022-07-12 | 2023-06-09 | 中南大学 | High-concentration fluorine-doped carbon dot and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565310A (en) * | 2016-03-02 | 2016-05-11 | 桂林理工大学 | Method for preparing fluorine doped graphene quantum dot with excellent optical properties |
| CN107200321A (en) * | 2017-06-13 | 2017-09-26 | 广西师范大学 | A kind of method of regulation and control graphene quantum dot luminescence generated by light |
-
2018
- 2018-07-23 CN CN201810809646.2A patent/CN108706579B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108706579A (en) | 2018-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Calabro et al. | Liquid-phase laser ablation synthesis of graphene quantum dots from carbon nano-onions: Comparison with chemical oxidation | |
| Xu et al. | Hydrochromic full-color MXene quantum dots through hydrogen bonding toward ultrahigh-efficiency white light-emitting diodes | |
| Mao et al. | Facile access to white fluorescent carbon dots toward light-emitting devices | |
| Dev et al. | Optical and field emission properties of ZnO nanorod arrays synthesized on zinc foils by the solvothermal route | |
| Liang et al. | Controlling the morphology of ZnO structures via low temperature hydrothermal method and their optoelectronic application | |
| CN108706579B (en) | Method for preparing fluorine-doped graphene quantum dots | |
| CN104743545A (en) | Preparation method of petroleum asphalt-based carbon quantum dot and application of petroleum asphalt-based carbon quantum dot prepared by method | |
| CN103288069A (en) | Method for preparing fluorinated graphene through microwave hydrothermal method | |
| CN105197917A (en) | Preparation method of nitrogen-doped graphene quantum dot dispersion liquid | |
| CN105800595A (en) | Nitrogen-doped graphene quantum dot and preparation method thereof | |
| CN105670617A (en) | Simple efficient one-step method for batch preparation of nitrogen-doped petroleum coke-based carbon quantum dots | |
| CN110294471A (en) | A kind of synthetic method of the nitrogen co-doped graphene quantum dot of boron | |
| Das et al. | Shape selective flower-like ZnO nanostructures prepared via structure-directing reagent free methods for efficient photocatalytic performance | |
| Behzadi et al. | One step synthesis of graphene quantum dots, graphene nanosheets and carbon nanospheres: Investigation of photoluminescence properties | |
| CN105733573A (en) | Electrolytic and nitrogen-doping one-step method for preparing petroleum coke-based carbon quantum dots | |
| CN108394885B (en) | Method for synthesizing solid carbon quantum dots by gas-phase detonation | |
| CN112961676A (en) | Preparation method of manganese-doped zinc germanate nano material | |
| Zhang et al. | Carbon nanodots-based nanocomposites with enhanced photocatalytic performance and photothermal effects | |
| Shi et al. | Preparation and photocatalytic activity of ZnO nanorods and ZnO/Cu 2O nanocomposites | |
| Iqbal et al. | Simple synthesis of WO3 based activated carbon co-doped CuS composites for photocatalytic applications | |
| CN105621407A (en) | Method for synthesizing sulfur-doped graphene quantum dots in one step | |
| CN110817850B (en) | Nitrogen-phosphorus co-doped graphene quantum dot and preparation method thereof | |
| CN109399581B (en) | Cuprous sulfide-tellurium nano material and preparation method thereof | |
| CN109987633A (en) | A kind of tungstic acid nano stick rich in Lacking oxygen, catalyst system and its preparation method and application | |
| Krasovska et al. | Obtaining a Well-Aligned ZnO Nanotube Array Using the Hydrothermal Growth Method/Labi Sakārtotu Zno Nanocauruļu Kopu Iegūšana, Izmantojot Hidrotermālo Metodi |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231110 Address after: Rooms 1806-1809, Building 2, Longguang Century, No. 8 Zhongkang Road, Qingxiu District, Nanning City, Guangxi Zhuang Autonomous Region, 530000 Patentee after: Nanning Precision Instruments and Meters Co.,Ltd. Address before: 541004 No. 15, Yucai Road, Guilin City, Guangxi Zhuang Autonomous Region Patentee before: Guangxi Normal University |